JP3698953B2 - Dielectric ceramic composition, ceramic capacitor using the same, and method for manufacturing the same - Google Patents

Dielectric ceramic composition, ceramic capacitor using the same, and method for manufacturing the same Download PDF

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JP3698953B2
JP3698953B2 JP2000098271A JP2000098271A JP3698953B2 JP 3698953 B2 JP3698953 B2 JP 3698953B2 JP 2000098271 A JP2000098271 A JP 2000098271A JP 2000098271 A JP2000098271 A JP 2000098271A JP 3698953 B2 JP3698953 B2 JP 3698953B2
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dielectric ceramic
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繁大 藤野
伸岳 平井
宗煕 金
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三星電機株式会社
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Description

【０００１】
【発明の属する技術分野】
本発明は、誘電体磁器組成物とそれを用いた磁器コンデンサ及びその製造方法に関し、特に、高周波数帯域において誘電体損失が小さく、しかも、安定した特性を有し、さらに、低温での焼成を実現することで電極材料に銅（Ｃｕ）、タングステン（Ｗ）等の卑金属、あるいはカーボン、グラファイト等の炭素系物質を用いることが可能になり、その結果、製造コストの大幅な低下、製品のコストダウンが可能になる誘電体磁器組成物とそれを用いた磁器コンデンサ及びその製造方法に関するものである。
【０００２】
【従来の技術】
従来、小型かつ大容量のコンデンサとして、セラミックスの誘電特性を利用したセラミックコンデンサが知られている。このセラミックコンデンサは、ルチル型のＴｉＯ2、ペロブスカイト型のＭｇＴｉＯ3、ＭｇＴｉＯ3、ＣａＴｉＯ3、ＳｒＴｉＯ3等の誘電体材料を単体、もしくはこれらを組み合わせることにより、所望の特性を有するコンデンサとされる。
【０００３】
セラミックコンデンサは、単層型と積層型に分類される。
単層セラミックコンデンサは、上述した材料の粉末を加圧成形して、例えば、ペレット（円板状）、ロッド（円筒状）、チップ（角型状）等の成形体とし、この成形体を大気中１２００〜１４００℃の温度で焼成して焼結体とし、この焼結体の表裏両面に電極を形成することにより得ることができる。
【０００４】
また、積層セラミックコンデンサは、上述した材料の粉末と有機バインダー及び有機溶剤を混練してスラリーとし、このスラリーをドクターブレード法によりシート状に成形し脱脂してグリーンシートとし、このグリーンシート上にＰｔやＰｄ等の貴金属からなる電極を印刷した後、これらのグリーンシートを厚み方向に重ね合わせ加圧して積層体とし、この積層体を大気中１２００〜１４００℃の温度で焼成することにより得ることができる。
【０００５】
【発明が解決しようとする課題】
ところで、上述した従来のセラミックコンデンサにおいては、電気的特性に優れた緻密な焼結体を得るためには、１２００〜１４００℃という高温度での焼成が必要になる。
特に、積層セラミックコンデンサにおいては、電極材料に卑金属を用いた場合、この卑金属が焼成時に酸化してセラミック層の間に高抵抗層を形成してしまうために、高温度でも安定なＰｔやＰｄ等の貴金属材料を用いる必要があり、低コスト化が難しいという問題点があった。
【０００６】
また、マイクロ波等の高周波数領域に適用する場合、誘電体損失が小さいものが望まれており、温度特性、品質係数（Ｑ）等の電気的特性に対してもより高特性かつ高信頼性のものが求められている。しかしながら、現在の誘電体材料ではこれらの要求に答えられるまでには至っていない。
【０００７】
本発明は、上記の事情に鑑みてなされたものであって、高周波数帯域における誘電体損失が小さく、しかも、安定した特性を有し、さらに、低温での焼成を実現することで卑金属や炭素系物質を電極材料に用いることができ、その結果、製造コストの大幅な低下、すなわち製品のコストダウンを図ることができる誘電体磁器組成物とそれを用いた磁器コンデンサ及びその製造方法を提供することを目的とする。
【０００８】
【課題を解決するための手段】
上記課題を解決するために、本発明は次のような誘電体磁器組成物とそれを用いた磁器コンデンサ及びその製造方法を提供した。
すなわち、請求項１記載の誘電体磁器組成物は、ＳｒxＢａ1-x（ＺｒyＴｉ1
-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加してなることを特徴としている。
【０００９】
この誘電体磁器組成物では、ＳｒxＢａ1-x（ＺｒyＴｉ1-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加したことにより、高い比誘電率、良好な温度特性、高い品質係数が実現可能になる。その結果、マイクロ波等の高周波数領域における特性が安定化し、高周波数領域における信頼性が向上する。
【００１０】
ここで、Ｓｒのモル比を０．８以上（８０ｍｏｌ％以上）としたのは、０．８未満（８０ｍｏｌ％未満）では、９２５〜１０８０℃の低温で焼成した場合、焼結性が低下することにより、良好な焼結体が得られないためである。
また、Ｔｉのモル比を０．１以下（１０ｍｏｌ％以下）としたのは、０．１（１０ｍｏｌ％）を越えると、品質係数（Ｑ）が低下するとともに、温度特性が負に大きくなってしまうためである。
【００１１】
ＭｎＯ2は、低温焼成を可能とするために焼結助剤として添加するものであり、その添加量は０．０５〜１５重量％が好ましい。その理由は、添加量が０．０５重量％未満では添加効果がなく、したがって、低温焼成において緻密な焼結体を得ることができず、また、１５重量％を越えると品質係数（Ｑ）が低下してしまうためである。
Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上の低融点金属酸化物は、温度特性を改善するために添加するものであり、その添加量は０．００１〜５重量％が好ましい。その理由は、添加量が０．００１重量％未満では温度特性の改善効果が得られず、また、５重量％を越えると品質係数（Ｑ）が低下するためである。
【００１２】
ガラス組成物は、９２５〜１０８０℃の低温焼成を可能とするために焼結助剤として添加するものであり、その添加量は０．５〜１５重量％が好ましい。その理由は、添加量が０．５重量％未満では焼結助剤としての効果が無く、したがって、低温焼成ができず、その結果、比誘電率、温度特性、品質係数が低下するためであり、また、１５重量％を越えると品質係数（Ｑ）が低下するためである。
【００１３】
ガラス組成物としては、添加しても特性に悪影響を及ぼすことが無く、主組成物であるＳｒxＢａ1-x（ＺｒyＴｉ1-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）とぬれ性が良く、しかも９２５〜１０８０℃の温度で軟化および／または溶融するガラスが好ましい。具体的には、ＺｎＯ−ＳｉＯ2系ガラス、Ｌｉ2Ｏ−Ａｌ2Ｏ3−ＳｉＯ2系ガラス等が好ましい。
【００１４】
請求項２記載の誘電体磁器組成物は、請求項１記載の誘電体磁器組成物において、前記主組成物に、ＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％添加してなることを特徴としている。
【００１５】
ＳｉＯ2は、温度特性を改善するために添加するものであり、その添加量は０．０１〜５重量％が好ましい。その理由は、添加量が０．０１重量％未満では温度特性の改善効果が得られず、また、５重量％を越えると品質係数（Ｑ）が低下するためである。
Ａｌ2Ｏ3は、品質係数（Ｑ）を改善するために添加するものであり、その添加量は０．０１〜５重量％が好ましい。その理由は、添加量が０．０１重量％未満では品質係数（Ｑ）の改善効果が得られず、また、５重量％を越えると温度特性が低下するからである。
【００１６】
請求項３記載の誘電体磁器組成物は、請求項１または２記載の誘電体磁器組成物において、前記主組成物に、希土類酸化物を０．００１〜２重量％添加してなることを特徴としている。
【００１７】
希土類酸化物は、温度特性の改善のために添加するものであり、その添加量は０．００１〜２重量％が好ましい。その理由は、添加量が０．００１重量％未満では温度特性の改善効果が得られず、また、２重量％を越えると品質係数（Ｑ）が低下するためである。
【００１８】
希土類酸化物としては、主組成物であるＳｒxＢａ1-x（ＺｒyＴｉ1-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）とぬれ性が良く、しかも粒界層に存在して焼結性を高めるものが好ましい。具体的には、Ｌａ2Ｏ3、ＣｅＯ2、Ｐｒ6Ｏ11、Ｎｄ2Ｏ3、Ｓｍ2Ｏ3、Ｄｙ2Ｏ3、Ｈｏ2Ｏ3、Ｅｒ2Ｏ3、Ｔｍ2Ｏ3、Ｙｂ2Ｏ3より選択された１種または２種以上を組み合わせたものが好ましい。
【００１９】
請求項６記載の磁器コンデンサは、請求項１ないし５のいずれか１項記載の誘電体磁器組成物からなる素子の両面に電極を形成してなることを特徴としている。
【００２０】
請求項７記載の磁器コンデンサは、請求項１ないし５のいずれか１項記載の誘電体磁器組成物からなるシート状の誘電体と、電極とを交互に積層してなることを特徴としている。
【００２１】
請求項８記載の磁器コンデンサは、請求項６または７記載の磁器コンデンサにおいて、前記電極を卑金属または炭素系物質としたことを特徴としている。
【００２２】
この磁器コンデンサでは、請求項１ないし５のいずれか１項記載の誘電体磁器組成物を用いたことにより、高周波数帯域における誘電体損失が小さく、安定した特性となる。これにより、特に高周波数帯域における信頼性が向上する。
また、前記誘電体磁器組成物を用いることにより、９２５〜１０８０℃の低温で焼成することが可能となる。その結果、内部電極に安価な卑金属または炭素系物質を用いて製造コストを低減することが可能になる。
【００２３】
前記卑金属としては、導体としての特性を有し、しかも信頼性の高い金属、例えば、銅（Ｃｕ）、ニッケル（Ｎｉ）、タングステン（Ｗ）、モリブデン（Ｍｏ）等の金属から選択された１種、または２種以上を含む金属が好ましい。
また、炭素系物質としては、カーボン（無定形炭素）、グラファイト（石墨、黒鉛）、またはこれらの混合物が好ましい。
【００２４】
請求項９記載の誘電体磁器組成物の製造方法は、ＳｒxＢａ1-x（ＺｒyＴｉ1-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加した粉体を、成形してバルク状もしくはシート状の成形体とし、この成形体を９２５〜１０８０℃の温度で焼成することを特徴としている。
【００２５】
この誘電体磁器組成物の製造方法では、ＳｒxＢａ1-x（ＺｒyＴｉ1-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加した粉体を、成形してバルク状もしくはシート状の成形体とし、この成形体を９２５〜１０８０℃の温度で焼成することにより、焼結助剤であるＭｎＯ2及びガラス組成物が〜１０８０℃の低温焼成過程において粒界層のぬれ性を向上させ、成形体中の粉末粒子同士を結合させるとともに、粉末粒子間の空隙を減少させて焼結を進行させる。これにより、９２５〜１０８０℃の低温で焼成した場合であっても、緻密で高強度の焼結体を得ることが可能になる。
【００２６】
請求項１０記載の誘電体磁器組成物の製造方法は、請求項９記載の誘電体磁器組成物の製造方法において、前記シート状の成形体の一主面に電極を形成し、次いで、この成形体を複数枚厚み方向に重ね合わせ加圧して積層体とし、この積層体を前記温度で焼成することを特徴としている。
【００２７】
この誘電体磁器組成物の製造方法では、シート状の成形体の一主面に電極を形成し、次いで、この成形体を複数枚厚み方向に重ね合わせ加圧して積層体とし、次いで、この積層体を前記温度で焼成することにより、内部電極材料にＰｔやＰｄ等の貴金属と比較して安価なＣｕ、Ｎｉ等の卑金属、または無定形炭素、グラファイト等の炭素系物質を用いることが可能になる。これにより、特性を低下させること無く低コスト化を図ることができる。
【００２８】
【発明の実施の形態】
本発明の誘電体磁器組成物とそれを用いた磁器コンデンサ及びその製造方法の各実施形態について図面に基づき説明する。
【００２９】
［第１の実施形態］
図１は本発明の第１の実施形態のセラミックコンデンサ（磁器コンデンサ）を示す断面図であり、図において、符号１はバルク状の誘電体、２は誘電体１の両面に形成された端子電極、３は端子電極２に接続されたリード線、４は誘電体１及び端子電極２を封止するエポキシ樹脂である。
【００３０】
誘電体１は、ＳｒxＢａ1-x（ＺｒyＴｉ1-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）（以下、単にＳＢＺＴと略記する）からなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラスフリット（ガラス組成物）を０．５〜１５重量％添加した材料組成からなる誘電体セラミックスである。
【００３１】
この誘電体１の材料組成を、前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％添加した材料組成、または、前記主組成物に希土類酸化物を０．００１〜２重量％添加した材料組成、あるいは、前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％、希土類酸化物を０．００１〜２重量％添加した材料組成、のいずれかとしてもよい。
【００３２】
端子電極２としては、導体としての特性を有し、しかも信頼性の高い電極材料、例えば、ＡｇもしくはＡｇ合金により構成されている。Ａｇ合金としては、例えば、９０Ａｇ−１０Ｐｄ等が好適に用いられる。
このＡｇもしくはＡｇ合金の替わりに、例えば、Ｃｕ、Ｎｉ、ＷまたはＭｏ、または、これらのうち２種以上を含む合金、あるいは、カーボン、グラファイト、これらの混合物を用いてもよい。
このセラミックコンデンサにおいては、比誘電率（ε）、品質係数（Ｑ）、温度特性（Ｔc）共、高周波領域においても安定している。
【００３３】
次に、このセラミックコンデンサの製造方法について説明する。
まず、粉末状のＳＢＺＴ、ＭｎＯ2、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上、ガラスフリット、ＳｉＯ2、Ａｌ2Ｏ3、希土類酸化物をそれぞれ所定量秤量した。
ここでは、粉末状のＳｒ0.95Ｂａ0.05（Ｚｒ0.95Ｔｉ0.05）Ｏ3、ＭｎＯ2、ＰｂＯ、ガラスフリット（ＺｎＯ−ＳｉＯ2系ガラスまたはＬｉ2Ｏ−Ａｌ2Ｏ3−ＳｉＯ2系ガラス）、ＳｉＯ2、Ａｌ2Ｏ3、Ｌａ2Ｏ3を表１及び表２に示す材料組成となるように秤量した。
【００３４】
【表１】

Figure 0003698953
【００３５】
【表２】
Figure 0003698953
【００３６】
次いで、これらの粉体を所定量の水（もしくはエタノール、アセトン等の有機溶媒）等の分散媒とともにボールミルに収容し、所定時間、例えば２４時間混合・粉砕し、その後脱水（もしくは脱エタノール、脱アセトン等の脱有機溶媒）・乾燥を行った。本発明の材料組成以外の組成の試料も作製し比較例とした（表１及び表２中では「※」で示してある）。
【００３７】
次いで、得られた乾燥粉末を５５０〜７５０℃の温度で０．５〜５．０時間、仮焼成し、次いで、ライカイ機（もしくは自動乳鉢）を用いて１〜２４時間粉砕し、所定の粒度の仮焼粉とした。
次いで、この仮焼粉に所定量の有機バインダーを加えた後、ライカイ機等を用いて均一に混合・造粒し、所定の粒度の造粒粉（団粒）とした。有機バインダーはＰＶＡ（polyvinyl alcohol）水溶液を用いた。有機バインダーとしては、エチルセルロース水溶液、アクリル樹脂水溶液（アクリルバインダー）等を用いてもよい。
【００３８】
次いで、成形機を用いて、この造粒粉を直径２０ｍｍ、厚さ２ｍｍのペレットに成形し、その後、大気中、９２５〜１０８０℃の温度で０．５〜１０．０時間焼成し、本実施形態の円板状の誘電体１を得た。なお、本発明の材料組成の試料を本発明の焼成温度範囲以外の温度で焼成し比較例とした（表１及び表２中では比較例を「※」で示してある）。
【００３９】
表３及び表４は、各試料における電気的特性を示したものである。なお、表３及び表４中では比較例を「※」で示してある。
【表３】
Figure 0003698953
【００４０】
【表４】
Figure 0003698953
【００４１】
ここでは、比誘電率（ε）は、２５℃において、１ＭＨｚ、１Ｖrmsの条件下で測定を行った。
品質係数（Ｑ）は、１ＭＨｚ、２５℃の条件下で測定した。
温度特性（Ｔc）は、２５℃での静電容量Ｃ１及び１２５℃での静電容量Ｃ２をそれぞれ測定し、これらの測定値を次式に代入することで温度特性（Ｔc）を算出した。
Ｔc（ｐｐｍ／℃）
＝（（Ｃ２−Ｃ１）×１０6）／（Ｃ１×（１２５−２５））
比抵抗（Ｒ（Ω・ｃｍ））は、２５℃において１０００Ｖの直流電圧を印加したときの１分後の電流値を測定し、これら電圧値及び電流値より比抵抗を算出した。
【００４２】
これらの表３及び表４から明かなように、本実施形態の試料によれば、比誘電率（ε）、品質係数（Ｑ）、温度特性（Ｔc）共、高周波領域においても安定していることが分かる。
一方、比較例の試料では、本実施形態の試料と比べて、比誘電率（ε）、温度特性（Ｔc）、品質係数（Ｑ）のいずれかが低下していることがわかる。
さらに、金属顕微鏡を用いて、本実施形態の試料の表面状態を観察したところ、粒界に空孔等が認められず、緻密な焼結体であることが確認された。
【００４３】
以上説明したように、本実施形態のセラミックコンデンサによれば、誘電体１を、ＳＢＺＴからなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラスフリットを０．５〜１５重量％添加し、必要に応じて前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％、希土類酸化物を０．００１〜２重量％添加した材料組成としたので、高い比誘電率、良好な温度特性、高い品質係数を実現することができる。したがって、マイクロ波等の高周波数帯域における特性を安定化させることができ、高周波数帯域における信頼性を向上させることができる。
【００４４】
本実施形態のセラミックコンデンサの製造方法によれば、ＳＢＺＴからなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加し、必要に応じて前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％、希土類酸化物を０．００１〜２重量％添加した粉体を、成形してバルク状の成形体とし、この成形体を９２５〜１０８０℃の温度で焼成するので、緻密で高強度の焼結体を低温焼成により作製することができる。
【００４５】
［第２の実施形態］
図２は本発明の第２の実施形態の積層セラミックコンデンサを示す断面図であり、図において、符号１１はシート状の誘電体層、１２は薄厚の内部電極、１３、１４は端子電極である。
この積層セラミックコンデンサでは、誘電体層１１を８層、内部電極１２を７層、交互に積層している。
【００４６】
誘電体層１１は、ＳＢＺＴからなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラスフリット（ガラス組成物）を０．５〜１５重量％添加した材料組成からなるシート状の誘電体セラミックスである。
【００４７】
この誘電体層１１の材料組成を、前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％添加した材料組成、または、前記主組成物に希土類酸化物を０．００１〜２重量％添加した材料組成、あるいは、前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％、希土類酸化物を０．００１〜２重量％添加した材料組成、のいずれかとしてもよい。
【００４８】
内部電極１２及び端子電極１３、１４は、導体としての特性を有し、しかも信頼性の高い電極材料、例えば、Ｃｕ、Ｎｉ、ＷまたはＭｏ、または、これらのうち２種以上を含む合金、あるいは、カーボン、グラファイト、これらの混合物が好適である。
この積層セラミックコンデンサにおいては、比誘電率（ε）、品質係数（Ｑ）、温度特性（Ｔc）共、高周波領域においても安定している。
【００４９】
次に、この積層セラミックコンデンサの製造方法について説明する。
まず、本実施形態の材料組成となるように、粉末状のＳＢＺＴ、ＭｎＯ2、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上、ガラス組成物、必要に応じてＳｉＯ2、Ａｌ2Ｏ3、希土類酸化物をそれぞれ所定量秤量し、これらの粉体を所定量の水（もしくはエタノール、アセトン等の有機溶媒）等の分散媒とともにボールミルに収容し、所定時間、例えば２４時間混合・粉砕し、その後脱水（もしくは脱エタノール、脱アセトン等の脱有機溶媒）・乾燥を行った。
【００５０】
次いで、この乾燥粉に所定量の有機バインダー及び有機溶剤を加えた後、ライカイ機、混練機等を用いて混練し、所定の粘度を有するスラリーとした。ここで、有機バインダーとしては、ＰＶＡ（polyvinyl alcohol）水溶液を用いた。有機バインダーは、エチルセルロース水溶液、アクリル樹脂水溶液（アクリルバインダー）等を用いてもよい。
次いで、ドクターブレード法により、このスラリーをシート状に成形し脱脂してグリーンシートとし、このグリーンシート上に、Ｃｕ、Ｎｉ、ＷまたはＭｏ、または、これらのうち２種以上を含む合金、あるいは、カーボン、グラファイト、カーボンとグラファイトの混合物を導電材料とする導電ペーストを所定のパターンに印刷し内部電極層とした。
【００５１】
この導電ペーストとしては、Ｃｕ粉末に、有機バインダー、分散剤、有機溶剤、必要に応じて還元剤、等を所定量加えた後に混練し、所定の粘度としたＣｕペーストの他、Ｎｉペースト、Ｗペースト、Ｍｏペースト、カーボン粉とグラファイト粉の混合粉体を用いたカーボンペースト等が好適に用いられる。
【００５２】
次いで、これらのグリーンシートを厚み方向に重ね合わせ、その後厚み方向に加圧して積層体とした。
次いで、この積層体を、Ｎ2ガス等の不活性ガス雰囲気中、あるいはＮ2−Ｈ2還元性ガス雰囲気中、９２５〜１０８０℃の温度で焼成し、その後、両側面に端子電極１３、１４を形成した。
以上により、誘電体層１１と内部電極１２とを交互に積層した積層セラミックコンデンサを作製することができた。
【００５３】
以上説明したように、本実施形態の積層セラミックコンデンサによれば、誘電体層１１を、ＳＢＺＴからなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加し、必要に応じて前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％、希土類酸化物を０．００１〜２重量％添加した材料組成としたので、高い比誘電率、良好な温度特性、高い品質係数を実現することができ、その結果、マイクロ波等の高周波数領域における特性を安定化させることができ、高周波数領域における信頼性を向上させることができる。
【００５４】
本実施形態の積層セラミックコンデンサの製造方法によれば、ＳＢＺＴからなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加し、必要に応じて前記主組成物にＳｉＯ2を０．０１〜５重量％、Ａｌ2Ｏ3を０．０１〜５重量％、希土類酸化物を０．００１〜２重量％添加したグリーンシート上に内部電極層を形成し、このグリーンシートを厚み方向に重ね合わせて積層体とし、この積層体を不活性ガス雰囲気中、あるいは還元性ガス雰囲気中、９２５〜１０８０℃の温度で焼成するので、内部電極１２の材料にＰｔやＰｄ等の貴金属と比較して安価な卑金属や炭素系物質を用いることができる。したがって、特性を低下させること無く低コスト化を図ることができる。
【００５５】
以上、本発明の誘電体磁器組成物とそれを用いた磁器コンデンサ及びその製造方法の各実施形態について図面に基づき説明してきたが、具体的な構成は上述した各実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲で設計の変更等が可能である。
例えば、第２の実施形態の積層セラミックコンデンサでは、誘電体層１１を８層、内部電極１２を７層、交互に積層した構成としたが、誘電体層１１及び内部電極１２それぞれの大きさや層数は、必要とされる容量や特性により適宜変更可能である。
【００５６】
【発明の効果】
以上説明した様に、本発明の誘電体磁器組成物によれば、ＳｒxＢａ1-x（ＺｒyＴｉ1-y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加したので、高い比誘電率、良好な温度特性、高い品質係数を実現することができ、その結果、マイクロ波等の高周波数領域における特性を安定化させることができ、高周波数領域における信頼性を向上させることができる。
【００５７】
本発明の磁器コンデンサによれば、本発明の誘電体磁器組成物からなる素子の両面に電極を形成したので、高周波数帯域における誘電体損失を小さくすることができる。その結果、マイクロ波等の高周波数帯域における特性を安定化させることができ、高周波数帯域における信頼性を向上させることができる。
また、電極に安価な卑金属または炭素系物質を用いれば、特性を低下させずに製造コストを低減することができる。
【００５８】
本発明の他の磁器コンデンサによれば、本発明の誘電体磁器組成物からなるシート状の誘電体と、電極とを交互に積層したので、高周波数帯域における誘電体損失を小さくすることができる。その結果、マイクロ波等の高周波数帯域における特性を安定化させることができ、高周波数帯域における信頼性を向上させることができる。
また、９２５〜１０８０℃の温度で焼成できるので、内部電極に安価な卑金属または炭素系物質を用いることができ、特性を低下させずに製造コストを低減することができる。
【００５９】
本発明の誘電体磁器組成物の製造方法によれば、ＳｒxＢａ1-x（ＺｒyＴｉ1- y）Ｏ3（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ2を０．０５〜１５重量％、Ｂｉ2Ｏ3、ＰｂＯ、Ｓｂ2Ｏ3より選択された１種または２種以上を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加した粉体を、成形してバルク状もしくはシート状の成形体とし、この成形体を９２５〜１０８０℃の温度で焼成するので、緻密で高強度の焼結体を低温かつ低コストで得ることができる。
【００６０】
本発明の他の誘電体磁器組成物の製造方法によれば、シート状の成形体の一主面に電極を形成し、次いで、この成形体を複数枚厚み方向に重ね合わせ加圧して積層体とし、次いで、この積層体を前記温度で焼成するので、内部電極材料にＰｔやＰｄ等の貴金属と比較して安価なＣｕ、Ｎｉ等の卑金属、または無定形炭素、グラファイト等の炭素系物質を用いることができ、緻密で高強度の積層体を低温かつ低コストで得ることができる。
【図面の簡単な説明】
【図１】 本発明の第１の実施形態の単層セラミックコンデンサを示す断面図である。
【図２】 本発明の第２の実施形態の積層セラミックコンデンサを示す断面図である。
【符号の説明】
１ バルク状の誘電体
２ 端子電極
３ リード線
４ エポキシ樹脂
１１ 誘電体層
１２ 内部電極
１３、１４ 端子電極[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dielectric ceramic composition, a ceramic capacitor using the same, and a method for manufacturing the same, and in particular, has a low dielectric loss in a high frequency band, has stable characteristics, and is fired at a low temperature. By realizing this, it becomes possible to use a base metal such as copper (Cu) or tungsten (W) or a carbon-based material such as carbon or graphite as the electrode material. As a result, the manufacturing cost is greatly reduced and the product cost is reduced. The present invention relates to a dielectric ceramic composition capable of being down, a ceramic capacitor using the same, and a method of manufacturing the same.
[0002]
[Prior art]
Conventionally, ceramic capacitors using the dielectric characteristics of ceramics are known as small-sized and large-capacity capacitors. This ceramic capacitor is a capacitor having desired characteristics by combining dielectric materials such as rutile type TiO 2 , perovskite type MgTiO 3 , MgTiO 3 , CaTiO 3 , SrTiO 3, or the like.
[0003]
Ceramic capacitors are classified into a single layer type and a multilayer type.
A single-layer ceramic capacitor is formed by pressing a powder of the above-mentioned material into a molded body such as a pellet (disk shape), a rod (cylindrical shape), or a chip (square shape). It can be obtained by firing at a temperature of 1200 to 1400 ° C. to form a sintered body and forming electrodes on both the front and back surfaces of the sintered body.
[0004]
The multilayer ceramic capacitor is made by kneading the above-mentioned material powder, an organic binder, and an organic solvent into a slurry. The slurry is formed into a sheet by a doctor blade method and degreased to obtain a green sheet. After printing an electrode made of a noble metal such as Pd or Pd, these green sheets are stacked and pressed in the thickness direction to form a laminate, and this laminate can be obtained by firing at a temperature of 1200 to 1400 ° C. in the atmosphere. it can.
[0005]
[Problems to be solved by the invention]
By the way, in the above-described conventional ceramic capacitor, firing at a high temperature of 1200 to 1400 ° C. is necessary in order to obtain a dense sintered body having excellent electrical characteristics.
In particular, in a multilayer ceramic capacitor, when a base metal is used as an electrode material, the base metal is oxidized during firing to form a high resistance layer between the ceramic layers. Therefore, stable Pt, Pd, etc. Therefore, there is a problem that it is difficult to reduce the cost.
[0006]
In addition, when applied to a high frequency region such as a microwave, a material having a small dielectric loss is desired, and higher electrical characteristics such as temperature characteristics and quality factor (Q) are more reliable and more reliable. Things are sought. However, current dielectric materials have yet to meet these requirements.
[0007]
The present invention has been made in view of the above circumstances, has a low dielectric loss in a high frequency band, has stable characteristics, and further realizes firing at a low temperature to realize base metal and carbon. Disclosed is a dielectric ceramic composition, a ceramic capacitor using the same, and a method of manufacturing the same, which can use a system material as an electrode material, resulting in a significant reduction in manufacturing cost, that is, cost reduction of a product. For the purpose.
[0008]
[Means for Solving the Problems]
In order to solve the above problems, the present invention provides the following dielectric ceramic composition, a ceramic capacitor using the dielectric ceramic composition, and a method for manufacturing the same.
That is, the dielectric ceramic composition of claim 1, wherein the, Sr x Ba 1-x ( Zr y Ti 1
-y ) O 3 (where 0.8 ≦ x ≦ 1, 0.9 ≦ y ≦ 1), 0.05 to 15% by weight of MnO 2 , Bi 2 O 3 , PbO, Sb One or two or more selected from 2 O 3 is added in an amount of 0.001 to 5% by weight and a glass composition is added in an amount of 0.5 to 15% by weight.
[0009]
In this dielectric ceramic composition, Sr x Ba 1-x ( Zr y Ti 1-y) O 3 ( however, 0.8 ≦ x ≦ 1,0.9 ≦ y ≦ 1) Main composition comprising, 0.05 to 15% by weight of MnO 2 , 0.001 to 5% by weight of one or more selected from Bi 2 O 3 , PbO and Sb 2 O 3 , and 0.5 to 15 of the glass composition By adding wt%, a high relative dielectric constant, good temperature characteristics, and a high quality factor can be realized. As a result, characteristics in a high frequency region such as a microwave are stabilized, and reliability in the high frequency region is improved.
[0010]
Here, the molar ratio of Sr is set to 0.8 or more (80 mol% or more). If it is less than 0.8 (less than 80 mol%), the sinterability deteriorates when fired at a low temperature of 925 to 1080 ° C. This is because a good sintered body cannot be obtained.
Moreover, the molar ratio of Ti is set to 0.1 or less (10 mol% or less). When 0.1 (10 mol%) is exceeded, the quality factor (Q) decreases and the temperature characteristics become negatively large. It is because it ends.
[0011]
MnO 2 is added as a sintering aid in order to enable low-temperature firing, and the addition amount is preferably 0.05 to 15% by weight. The reason is that if the addition amount is less than 0.05% by weight, there is no effect of addition, and therefore a dense sintered body cannot be obtained in low-temperature firing, and if it exceeds 15% by weight, the quality factor (Q) is increased. It is because it will fall.
One or more low melting point metal oxides selected from Bi 2 O 3 , PbO, and Sb 2 O 3 are added to improve temperature characteristics, and the added amount is 0.001 to 0.001. 5% by weight is preferred. The reason is that if the added amount is less than 0.001% by weight, the effect of improving the temperature characteristics cannot be obtained, and if it exceeds 5% by weight, the quality factor (Q) is lowered.
[0012]
The glass composition is added as a sintering aid in order to enable low-temperature firing at 925 to 1080 ° C., and the addition amount is preferably 0.5 to 15% by weight. The reason is that if the addition amount is less than 0.5% by weight, there is no effect as a sintering aid, and therefore low-temperature firing cannot be performed, resulting in a decrease in relative permittivity, temperature characteristics, and quality factor. In addition, if it exceeds 15% by weight, the quality factor (Q) is lowered.
[0013]
The glass composition, without adversely affecting the even characteristics by adding a primary composition Sr x Ba 1-x (Zr y Ti 1-y) O 3 ( however, 0.8 ≦ x ≦ 1 0.9 ≦ y ≦ 1), which has good wettability, and is preferably softened and / or melted at a temperature of 925 to 1080 ° C. Specifically, ZnO—SiO 2 glass, Li 2 O—Al 2 O 3 —SiO 2 glass, and the like are preferable.
[0014]
The dielectric ceramic composition according to claim 2 is the dielectric ceramic composition according to claim 1, wherein the main composition is composed of 0.01 to 5% by weight of SiO 2 and 0.01 to 5% of Al 2 O 3 . It is characterized by adding 5% by weight.
[0015]
SiO 2 is added to improve temperature characteristics, and the addition amount is preferably 0.01 to 5% by weight. The reason is that if the addition amount is less than 0.01% by weight, the effect of improving the temperature characteristics cannot be obtained, and if it exceeds 5% by weight, the quality factor (Q) decreases.
Al 2 O 3 is added to improve the quality factor (Q), and the addition amount is preferably 0.01 to 5% by weight. The reason is that if the addition amount is less than 0.01% by weight, the effect of improving the quality factor (Q) cannot be obtained, and if it exceeds 5% by weight, the temperature characteristics are deteriorated.
[0016]
The dielectric ceramic composition according to claim 3 is characterized in that in the dielectric ceramic composition according to claim 1 or 2, 0.001 to 2% by weight of a rare earth oxide is added to the main composition. It is said.
[0017]
The rare earth oxide is added to improve temperature characteristics, and the amount added is preferably 0.001 to 2% by weight. The reason is that if the added amount is less than 0.001% by weight, the effect of improving the temperature characteristics cannot be obtained, and if it exceeds 2% by weight, the quality factor (Q) is lowered.
[0018]
Examples of the rare earth oxide, Sr x Ba 1-x ( Zr y Ti 1-y) O 3 ( however, 0.8 ≦ x ≦ 1,0.9 ≦ y ≦ 1) and the wettability is the main composition What is good and exists in a grain boundary layer and improves sinterability is preferable. Specifically, La 2 O 3 , CeO 2 , Pr 6 O 11 , Nd 2 O 3 , Sm 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 a combination of one or more selected from the preferred.
[0019]
A ceramic capacitor according to a sixth aspect is characterized in that electrodes are formed on both surfaces of an element made of the dielectric ceramic composition according to any one of the first to fifth aspects.
[0020]
According to a seventh aspect of the present invention, there is provided a ceramic capacitor characterized in that a sheet-like dielectric made of the dielectric ceramic composition according to any one of the first to fifth aspects and electrodes are alternately laminated.
[0021]
A ceramic capacitor according to an eighth aspect is the ceramic capacitor according to the sixth or seventh aspect, wherein the electrode is a base metal or a carbon-based material.
[0022]
In this ceramic capacitor, since the dielectric ceramic composition according to any one of claims 1 to 5 is used, dielectric loss in a high frequency band is small and stable characteristics are obtained. This improves the reliability especially in the high frequency band.
Further, by using the dielectric ceramic composition, it is possible to fire at a low temperature of 925 to 1080 ° C. As a result, it is possible to reduce the manufacturing cost by using an inexpensive base metal or carbon-based material for the internal electrode.
[0023]
The base metal has a characteristic as a conductor and has high reliability, for example, one selected from metals such as copper (Cu), nickel (Ni), tungsten (W), and molybdenum (Mo). Or the metal containing 2 or more types is preferable.
The carbon-based material is preferably carbon (amorphous carbon), graphite (graphite, graphite), or a mixture thereof.
[0024]
The method according to claim 9 dielectric ceramic composition as set forth in, Sr x Ba 1-x ( Zr y Ti 1-y) O 3 ( however, 0.8 ≦ x ≦ 1,0.9 ≦ y ≦ 1) A main composition comprising: 0.05 to 15% by weight of MnO 2 , 0.001 to 5% by weight of one or more selected from Bi 2 O 3 , PbO and Sb 2 O 3 , glass composition A powder added with 0.5 to 15% by weight of the product is molded into a bulk or sheet-shaped molded body, and the molded body is fired at a temperature of 925 to 1080 ° C.
[0025]
In this manufacturing method of a dielectric ceramic composition, Sr x Ba 1-x ( Zr y Ti 1-y) O 3 ( however, 0.8 ≦ x ≦ 1,0.9 ≦ y ≦ 1) main composition consisting In addition, 0.05 to 15% by weight of MnO 2 , 0.001 to 5% by weight of one or more selected from Bi 2 O 3 , PbO and Sb 2 O 3 , and a glass composition of 0. The powder added with 5 to 15% by weight is formed into a bulk or sheet-like molded body, and this molded body is fired at a temperature of 925 to 1080 ° C., so that MnO 2 as a sintering aid and glass are sintered. The composition improves the wettability of the grain boundary layer in the low-temperature firing process at −1080 ° C., bonds the powder particles in the molded body, and reduces the voids between the powder particles to advance the sintering. Thereby, even when fired at a low temperature of 925 to 1080 ° C., a dense and high-strength sintered body can be obtained.
[0026]
The method for producing a dielectric ceramic composition according to claim 10 is the method for producing a dielectric ceramic composition according to claim 9, wherein an electrode is formed on one main surface of the sheet-like molded body, and then the molding is performed. A plurality of bodies are stacked and pressed in the thickness direction to form a laminate, and the laminate is fired at the above temperature.
[0027]
In this method for producing a dielectric ceramic composition, an electrode is formed on one main surface of a sheet-like molded body, and then a plurality of the molded bodies are stacked and pressed in the thickness direction to form a laminated body. By firing the body at the above temperature, it is possible to use inexpensive base metals such as Cu and Ni, or carbon-based materials such as amorphous carbon and graphite as the internal electrode material compared with noble metals such as Pt and Pd. Become. Thereby, cost reduction can be achieved without deteriorating characteristics.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of a dielectric ceramic composition of the present invention, a ceramic capacitor using the same, and a manufacturing method thereof will be described with reference to the drawings.
[0029]
[First Embodiment]
FIG. 1 is a cross-sectional view showing a ceramic capacitor (a porcelain capacitor) according to a first embodiment of the present invention. In the figure, reference numeral 1 denotes a bulk dielectric, and 2 denotes a terminal electrode formed on both surfaces of the dielectric 1. Reference numeral 3 denotes a lead wire connected to the terminal electrode 2, and 4 denotes an epoxy resin that seals the dielectric 1 and the terminal electrode 2.
[0030]
The dielectric 1 is a Sr x Ba 1-x (Zr y Ti 1-y) O 3 ( however, 0.8 ≦ x ≦ 1,0.9 ≦ y ≦ 1) ( hereinafter, abbreviated as SBZT) In the main composition, 0.05 to 15 wt% of MnO 2 , 0.001 to 5 wt% of one or more selected from Bi 2 O 3 , PbO and Sb 2 O 3 , glass frit ( It is a dielectric ceramic comprising a material composition to which 0.5 to 15% by weight of a glass composition is added.
[0031]
The material composition of the dielectric 1 is a material composition obtained by adding 0.01 to 5% by weight of SiO 2 and 0.01 to 5% by weight of Al 2 O 3 to the main composition, or a rare earth to the main composition. A material composition in which 0.001 to 2 % by weight of an oxide is added, or 0.01 to 5% by weight of SiO 2 , 0.01 to 5% by weight of Al 2 O 3, and a rare earth oxide in the main composition. Any one of 0.001 to 2% by weight added material composition may be used.
[0032]
The terminal electrode 2 is made of a highly reliable electrode material, for example, Ag or an Ag alloy, which has characteristics as a conductor. As an Ag alloy, for example, 90Ag-10Pd is preferably used.
Instead of this Ag or Ag alloy, for example, Cu, Ni, W or Mo, an alloy containing two or more of these, carbon, graphite, or a mixture thereof may be used.
In this ceramic capacitor, the relative dielectric constant (ε), the quality factor (Q), and the temperature characteristic (T c ) are stable even in the high frequency region.
[0033]
Next, a method for manufacturing this ceramic capacitor will be described.
First, powdery SBZT, MnO 2 , Bi 2 O 3 , PbO, Sb 2 O 3 , one or more selected from glass frit, SiO 2 , Al 2 O 3 , rare earth oxide, respectively Weighed.
Here, powdered Sr 0.95 Ba 0.05 (Zr 0.95 Ti 0.05 ) O 3 , MnO 2 , PbO, glass frit (ZnO—SiO 2 glass or Li 2 O—Al 2 O 3 —SiO 2 glass), SiO 2 , Al 2 O 3 and La 2 O 3 were weighed so as to have the material compositions shown in Tables 1 and 2.
[0034]
[Table 1]
Figure 0003698953
[0035]
[Table 2]
Figure 0003698953
[0036]
Next, these powders are placed in a ball mill together with a predetermined amount of water (or an organic solvent such as ethanol or acetone) in a ball mill, mixed and pulverized for a predetermined time, for example, 24 hours, and then dehydrated (or deethanolated, dehydrated). (Deorganic solvent such as acetone) and drying. Samples having compositions other than the material composition of the present invention were also prepared as comparative examples (indicated by “*” in Tables 1 and 2).
[0037]
Next, the obtained dry powder is calcined for 0.5 to 5.0 hours at a temperature of 550 to 750 ° C., and then pulverized for 1 to 24 hours using a lye mill (or automatic mortar) to obtain a predetermined particle size. The calcined powder was used.
Next, after adding a predetermined amount of an organic binder to the calcined powder, the mixture was uniformly mixed and granulated using a reiki machine or the like to obtain a granulated powder (aggregate) having a predetermined particle size. As the organic binder, a PVA (polyvinyl alcohol) aqueous solution was used. As the organic binder, an ethyl cellulose aqueous solution, an acrylic resin aqueous solution (acrylic binder) or the like may be used.
[0038]
Next, this granulated powder is formed into pellets having a diameter of 20 mm and a thickness of 2 mm using a molding machine, and then fired in the atmosphere at a temperature of 925 to 1080 ° C. for 0.5 to 10.0 hours. A disk-shaped dielectric 1 having a shape was obtained. In addition, the sample of the material composition of the present invention was fired at a temperature outside the firing temperature range of the present invention to make a comparative example (in Table 1 and Table 2, the comparative example is indicated by “*”).
[0039]
Tables 3 and 4 show the electrical characteristics of each sample. In Tables 3 and 4, comparative examples are indicated by “*”.
[Table 3]
Figure 0003698953
[0040]
[Table 4]
Figure 0003698953
[0041]
Here, the relative dielectric constant (ε) was measured under the conditions of 1 MHz and 1 V rms at 25 ° C.
The quality factor (Q) was measured under conditions of 1 MHz and 25 ° C.
Temperature characteristics (T c), the electrostatic capacity C2 of the electrostatic capacitance C1 and 125 ° C. at 25 ° C. was measured, calculates the temperature characteristic (T c) by substituting these measured values into the following formula did.
T c (ppm / ° C)
= ((C2-C1) × 10 6 ) / (C1 × (125-25))
The specific resistance (R (Ω · cm)) was determined by measuring the current value after 1 minute when a DC voltage of 1000 V was applied at 25 ° C., and calculating the specific resistance from these voltage value and current value.
[0042]
As is clear from these Tables 3 and 4, according to the sample of this embodiment, the relative permittivity (ε), the quality factor (Q), and the temperature characteristic (T c ) are stable even in the high frequency region. I understand that.
On the other hand, in the sample of the comparative example, it can be seen that any of the relative dielectric constant (ε), the temperature characteristic (T c ), and the quality factor (Q) is lower than that of the sample of the present embodiment.
Furthermore, when the surface state of the sample of this embodiment was observed using a metal microscope, no pores or the like were observed at the grain boundaries, and it was confirmed to be a dense sintered body.
[0043]
As described above, according to the ceramic capacitor of the present embodiment, the dielectric 1 is composed of a main composition composed of SBZT, 0.05 to 15% by weight of MnO 2 , Bi 2 O 3 , PbO, Sb 2 O. One or two or more selected from 3 is added in an amount of 0.001 to 5% by weight and glass frit is added in an amount of 0.5 to 15% by weight. If necessary, SiO 2 is added to the main composition in an amount of 0.01 to 5%. wt%, Al 2 O 3 0.01 to 5 wt%, since the material composition obtained by adding a rare earth oxide 0.001-2 wt%, realizing a high dielectric constant, good temperature characteristics, high quality factor can do. Therefore, characteristics in a high frequency band such as a microwave can be stabilized, and reliability in the high frequency band can be improved.
[0044]
According to the method for producing a ceramic capacitor of the present embodiment, the main composition composed of SBZT contains one or more selected from 0.05 to 15% by weight of MnO 2 , Bi 2 O 3 , PbO, and Sb 2 O 3. Two or more kinds are added in an amount of 0.001 to 5% by weight, and a glass composition is added in an amount of 0.5 to 15% by weight. If necessary, 0.01 to 5% by weight of SiO 2 and Al 2 O 3 are added to the main composition. Is formed into a bulk-shaped molded body, and the molded body is fired at a temperature of 925 to 1080 ° C. A dense and high-strength sintered body can be produced by low-temperature firing.
[0045]
[Second Embodiment]
FIG. 2 is a cross-sectional view showing a multilayer ceramic capacitor according to a second embodiment of the present invention. In the figure, reference numeral 11 denotes a sheet-like dielectric layer, 12 denotes a thin internal electrode, and 13 and 14 denote terminal electrodes. .
In this multilayer ceramic capacitor, eight dielectric layers 11 and seven internal electrodes 12 are alternately laminated.
[0046]
The dielectric layer 11 has a main composition composed of SBZT, 0.05 to 15% by weight of MnO 2, and one or more selected from Bi 2 O 3 , PbO, and Sb 2 O 3 are 0.001. It is a sheet-like dielectric ceramic having a material composition to which 5% by weight and 0.5 to 15% by weight of glass frit (glass composition) are added.
[0047]
The material composition of the dielectric layer 11 is a material composition obtained by adding 0.01 to 5% by weight of SiO 2 and 0.01 to 5% by weight of Al 2 O 3 to the main composition, or to the main composition. A material composition in which 0.001 to 2 wt% of rare earth oxide is added, or 0.01 to 5 wt% of SiO 2 and 0.01 to 5 wt% of Al 2 O 3 in the main composition, rare earth oxide It is good also as either of the material composition which added 0.001-2 weight%.
[0048]
The internal electrode 12 and the terminal electrodes 13 and 14 have characteristics as conductors and are highly reliable electrode materials such as Cu, Ni, W or Mo, or alloys containing two or more of these, or Carbon, graphite and mixtures thereof are preferred.
In this multilayer ceramic capacitor, the relative dielectric constant (ε), the quality factor (Q), and the temperature characteristic (T c ) are stable even in the high frequency region.
[0049]
Next, a method for manufacturing this multilayer ceramic capacitor will be described.
First, one or more selected from powdered SBZT, MnO 2 , Bi 2 O 3 , PbO, and Sb 2 O 3 , a glass composition, and a glass composition, as necessary, so as to have the material composition of the present embodiment SiO 2 , Al 2 O 3 , and rare earth oxides are weighed in predetermined amounts, and these powders are placed in a ball mill together with a predetermined amount of a dispersion medium such as water (or an organic solvent such as ethanol or acetone) for a predetermined time. For example, the mixture was mixed and pulverized for 24 hours, followed by dehydration (or deorganic solvent such as deethanol and deacetone) and drying.
[0050]
Next, a predetermined amount of an organic binder and an organic solvent were added to the dried powder, and the mixture was kneaded using a laika machine, a kneader or the like to obtain a slurry having a predetermined viscosity. Here, a PVA (polyvinyl alcohol) aqueous solution was used as the organic binder. As the organic binder, an ethyl cellulose aqueous solution, an acrylic resin aqueous solution (acrylic binder) or the like may be used.
Next, by a doctor blade method, this slurry is formed into a sheet shape and degreased to obtain a green sheet. On this green sheet, Cu, Ni, W or Mo, or an alloy containing two or more of these, or A conductive paste using carbon, graphite, or a mixture of carbon and graphite as a conductive material was printed in a predetermined pattern to form an internal electrode layer.
[0051]
As this conductive paste, an organic binder, a dispersing agent, an organic solvent, and a reducing agent as required are added to Cu powder in a predetermined amount and then kneaded to obtain a predetermined viscosity, as well as Ni paste, W Paste, Mo paste, carbon paste using a mixed powder of carbon powder and graphite powder, and the like are preferably used.
[0052]
Next, these green sheets were superposed in the thickness direction, and then pressed in the thickness direction to obtain a laminate.
Next, this laminate is fired in an inert gas atmosphere such as N 2 gas or in an N 2 —H 2 reducing gas atmosphere at a temperature of 925 to 1080 ° C. After that, terminal electrodes 13 and 14 are formed on both side surfaces. Formed.
As described above, a multilayer ceramic capacitor in which the dielectric layers 11 and the internal electrodes 12 were alternately laminated could be manufactured.
[0053]
As described above, according to the multilayer ceramic capacitor of this embodiment, the dielectric layer 11 is made of SBZT as the main composition, MnO 2 is 0.05 to 15 wt%, Bi 2 O 3 , PbO, Sb. 2 O 3 1, two or more of 0.001-5 wt% selected from the, the glass composition was added 0.5 to 15 wt%, a SiO 2 to the main composition optionally 0. 01-5 wt%, an Al 2 O 3 0.01 to 5 wt%, since the material composition obtained by adding a rare earth oxide 0.001-2% by weight, high dielectric constant, good temperature characteristics, high quality A coefficient can be realized, and as a result, characteristics in a high frequency region such as a microwave can be stabilized, and reliability in a high frequency region can be improved.
[0054]
According to the method for manufacturing a multilayer ceramic capacitor of the present embodiment, the main composition composed of SBZT contains 0.05% to 15% by weight of MnO 2 , Bi 2 O 3 , PbO, Sb 2 O 3. Alternatively, two or more of 0.001 to 5% by weight and a glass composition of 0.5 to 15% by weight are added, and if necessary, SiO 2 is added to the main composition by 0.01 to 5% by weight, Al 2 O. An internal electrode layer is formed on a green sheet added with 0.01 to 5% by weight of 3 and 0.001 to 2% by weight of rare earth oxide, and this green sheet is laminated in the thickness direction to form a laminate. Since the body is baked at a temperature of 925 to 1080 ° C. in an inert gas atmosphere or a reducing gas atmosphere, the base electrode 12 is made of a base metal or carbon-based material that is less expensive than noble metals such as Pt and Pd. Can be used. Therefore, the cost can be reduced without degrading the characteristics.
[0055]
As mentioned above, although each embodiment of the dielectric ceramic composition of this invention, the ceramic capacitor using the same, and its manufacturing method has been demonstrated based on drawing, a concrete structure is not limited to each embodiment mentioned above. The design can be changed without departing from the scope of the present invention.
For example, in the multilayer ceramic capacitor of the second embodiment, eight dielectric layers 11 and seven layers of internal electrodes 12 are alternately stacked, but the size and layers of the dielectric layers 11 and internal electrodes 12 are different. The number can be appropriately changed according to the required capacity and characteristics.
[0056]
【The invention's effect】
As described above, according to the dielectric ceramic composition of the present invention, Sr x Ba 1-x ( Zr y Ti 1-y) O 3 ( however, 0.8 ≦ x ≦ 1,0.9 ≦ y ≦ 1), 0.001 to 5% by weight of one or more selected from 0.05 to 15% by weight of MnO 2 and Bi 2 O 3 , PbO and Sb 2 O 3 Since 0.5 to 15% by weight of glass composition is added, high dielectric constant, good temperature characteristics, and high quality factor can be realized. As a result, characteristics in high frequency range such as microwaves are stabilized. And reliability in a high frequency region can be improved.
[0057]
According to the ceramic capacitor of the present invention, since the electrodes are formed on both surfaces of the element made of the dielectric ceramic composition of the present invention, the dielectric loss in the high frequency band can be reduced. As a result, characteristics in a high frequency band such as a microwave can be stabilized, and reliability in the high frequency band can be improved.
If an inexpensive base metal or carbon-based material is used for the electrode, the manufacturing cost can be reduced without deteriorating the characteristics.
[0058]
According to the other ceramic capacitor of the present invention, since the sheet-like dielectric made of the dielectric ceramic composition of the present invention and the electrode are alternately laminated, the dielectric loss in the high frequency band can be reduced. . As a result, characteristics in a high frequency band such as a microwave can be stabilized, and reliability in the high frequency band can be improved.
Moreover, since it can bake at the temperature of 925-1080 degreeC, an inexpensive base metal or a carbon-type substance can be used for an internal electrode, and manufacturing cost can be reduced, without reducing a characteristic.
[0059]
According to the production method of a dielectric ceramic composition of the present invention, Sr x Ba 1-x ( Zr y Ti 1- y) O 3 ( however, 0.8 ≦ x ≦ 1,0.9 ≦ y ≦ 1) A main composition comprising: 0.05 to 15% by weight of MnO 2 , 0.001 to 5% by weight of one or more selected from Bi 2 O 3 , PbO and Sb 2 O 3 , glass composition The powder added with 0.5 to 15% by weight of the product is molded into a bulk or sheet-like molded body, and this molded body is fired at a temperature of 925 to 1080 ° C., so dense and high-strength sintering The body can be obtained at low temperature and low cost.
[0060]
According to another method for producing a dielectric ceramic composition of the present invention, an electrode is formed on one main surface of a sheet-like molded body, and then a plurality of the molded bodies are stacked and pressed in the thickness direction to form a laminate. Then, since this laminate is fired at the above temperature, a base metal such as Cu or Ni, which is less expensive than a noble metal such as Pt or Pd, or a carbon-based material such as amorphous carbon or graphite is used as the internal electrode material. A dense and high-strength laminate can be obtained at low temperature and low cost.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a single-layer ceramic capacitor according to a first embodiment of the present invention.
FIG. 2 is a cross-sectional view showing a multilayer ceramic capacitor according to a second embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Bulk dielectric 2 Terminal electrode 3 Lead wire 4 Epoxy resin 11 Dielectric layer 12 Internal electrode 13, 14 Terminal electrode

Claims (9)

ＳｒｘＢａ１−ｘ（ＺｒｙＴｉ１−ｙ）Ｏ３（ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ２を０．０５〜１５重量％、Ｓｂ ２ Ｏ ３ を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加してなることを特徴とする誘電体磁器組成物。In a main composition composed of Sr x Ba 1-x (Zr y Ti 1-y ) O 3 (where 0.8 ≦ x ≦ 1, 0.9 ≦ y ≦ 1), 0.05 to 15 MnO 2 is added to the main composition. A dielectric ceramic composition comprising: wt%, 0.001 to 5 wt% of Sb 2 O 3 and 0.5 to 15 wt% of a glass composition. 前記主組成物に、ＳｉＯ２を０．０１〜５重量％、Ａｌ２Ｏ３を０．０１〜５重量％添加してなることを特徴とする請求項１記載の誘電体磁器組成物。The main to the composition, the SiO 2 0.01 to 5 wt%, the dielectric ceramic composition of claim 1, wherein the Al 2 O 3, characterized by comprising adding 0.01 to 5 wt%. 前記主組成物に、希土類酸化物を０．００１〜２重量％添加してなることを特徴とする請求項１または２記載の誘電体磁器組成物。  3. The dielectric ceramic composition according to claim 1, wherein 0.002 to 2% by weight of rare earth oxide is added to the main composition. 前記希土類酸化物は、ＬａThe rare earth oxide is La ２2 ＯO ３3 、ＣｅＯ, CeO ２2 、Ｐｒ, Pr ６6 ＯO １１11 、Ｎｄ, Nd ２2 ＯO ３3 、Ｓｍ, Sm ２2 ＯO ３3 、Ｄｙ, Dy ２2 ＯO ３3 、Ｈｏ, Ho ２2 ＯO ３3 、Ｅｒ, Er ２2 ＯO ３3 、Ｔｍ, Tm ２2 ＯO ３3 、Ｙｂ, Yb ２2 ＯO ３3 より選択された１種または２種以上であることを特徴とする請求項３記載の誘電体磁器組成物。4. The dielectric ceramic composition according to claim 3, wherein the dielectric ceramic composition is one or more selected. 請求項１ないし４のいずれか１項記載の誘電体磁器組成物からなる素子の両面に電極を形成してなることを特徴とする磁器コンデンサ。A ceramic capacitor comprising electrodes formed on both sides of an element made of the dielectric ceramic composition according to any one of claims 1 to 4. 請求項１ないし４のいずれか１項記載の誘電体磁器組成物からなるシート状の誘電体と電極とを交互に積層してなることを特徴とする磁器コンデンサ。5. A ceramic capacitor comprising a sheet-like dielectric made of the dielectric ceramic composition according to any one of claims 1 to 4 and electrodes laminated alternately. 前記電極は、卑金属または炭素系物質からなることを特徴とする請求項５または６記載の磁器コンデンサ。The ceramic capacitor according to claim 5 or 6, wherein the electrode is made of a base metal or a carbon-based material. ＳｒSr ｘx ＢａBa １−ｘ1-x （Ｚｒ(Zr ｙy ＴｉTi １−ｙ1-y ）Ｏ) O ３3 （ただし、０．８≦ｘ≦１、０．９≦ｙ≦１）からなる主組成物に、ＭｎＯ(However, 0.8 ≦ x ≦ 1, 0.9 ≦ y ≦ 1) ２2 を０．０５〜１５重量％、Ｓｂ0.05 to 15% by weight, Sb ２2 ＯO ３3 を０．００１〜５重量％、ガラス組成物を０．５〜１５重量％添加した粉体を、成形してバルク状もしくはシート状の成形体とし、この成形体を９２５〜１０８０℃の温度で焼成することを特徴とする誘電体磁器組成物の製造方法。Is added to 0.001 to 5% by weight and a glass composition is added to 0.5 to 15% by weight to form a bulk or sheet-like molded body, and the molded body is at a temperature of 925 to 1080 ° C. A method for producing a dielectric ceramic composition, comprising firing. 前記シート状の成形体の一主面に電極を形成し、次いで、この成形体を複数枚厚み方向に重ね合わせ加圧して積層体とし、この積層体を前記温度で焼成することを特徴とする請求項８記載の誘電体磁器組成物の製造方法。An electrode is formed on one main surface of the sheet-like molded body, and then a plurality of the molded bodies are stacked and pressed in the thickness direction to form a laminated body, and the laminated body is fired at the temperature. The method for producing a dielectric ceramic composition according to claim 8.
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